[go: up one dir, main page]

WO2025007088A1 - Systèmes et procédés de traitement d'eau contaminée utilisée en tant que source d'hydrogène - Google Patents

Systèmes et procédés de traitement d'eau contaminée utilisée en tant que source d'hydrogène Download PDF

Info

Publication number
WO2025007088A1
WO2025007088A1 PCT/US2024/036304 US2024036304W WO2025007088A1 WO 2025007088 A1 WO2025007088 A1 WO 2025007088A1 US 2024036304 W US2024036304 W US 2024036304W WO 2025007088 A1 WO2025007088 A1 WO 2025007088A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
hydrogen
halogen
contaminated water
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/036304
Other languages
English (en)
Inventor
Harikrishnan Parthasarathy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wp&e Technologies And Solutions LLC
Original Assignee
Wp&e Technologies And Solutions LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wp&e Technologies And Solutions LLC filed Critical Wp&e Technologies And Solutions LLC
Publication of WO2025007088A1 publication Critical patent/WO2025007088A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B01D53/685—Halogens or halogen compounds by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20405—Monoamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20421—Primary amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20478—Alkanolamines
    • B01D2252/20484—Alkanolamines with one hydroxyl group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/009—Apparatus with independent power supply, e.g. solar cells, windpower or fuel cells

Definitions

  • FIELD FIELD
  • This disclosure is directed to systems and methods for treating contaminated water as a source for hydrogen and, in particular, to systems and methods for treating contaminated water to generate, capture, and/or utilize gaseous byproducts, such as hydrogen gas that result from the treatment of contaminated water.
  • BACKGROUND Electrolysis is a known method for treating water to generate, capture, and/or utilize a gaseous byproduct. Electrolysis systems and methods use electricity to split water molecules into hydrogen and oxygen gas. However, electrolysis often times requires a clean aqueous stream(s), or water, that has been deionized, meaning all or substantially all impurities, minerals, and electrically-charged particles must be removed before the water can be used.
  • Petroleum refining effluent which is the contaminated water discharged from petroleum refineries, is typically burned to remove hydrocarbon components therein before it is released into the environment.
  • Contaminated “discharge water” e.g., water volumes or streams periodically or continuously discharged to the sea or other body(ies) of water
  • discharge water e.g., water volumes or streams periodically or continuously discharged to the sea or other body(ies) of water
  • produced water or “dirty water” production facilities and/or from “produced water” or “dirty water” processing facilities
  • discharge water that is emitted from remote, “dirty water” production facilities, for example, from off shore oil or gas platforms, is highly regulated or becoming highly regulated.
  • oil or gas wells are considered “dirty water” “production facilities” in that they mainly or primarily produce/extract water that is not readily obtainable or that has been sequestered in a substrate or material, and that happens to have a small but economically valuable fraction that is oil and gas.
  • removing, capturing, and redirecting the oil and/or gas fraction is often time associated with one or more related industrial channels-of-trade, and/or associated with specific regulations and understandings of what is acceptable.
  • processing “dirty water”, e.g., what remains of the “produced water” after processing for the oil and gas, is often times associated with its own, different industrial channels-of-trade and/or with different regulations and understandings of what is acceptable.
  • Patent Application Docket No.067862.00033 [0010] Accordingly, there is a need in the art for systems and methods for treating contaminated water of all types to generate, capture, and/or utilize gaseous byproducts, particularly, hydrogen.
  • Existing approaches have limitations in terms of energy consumption, process complexity, and byproduct management, and none of these approaches have provided a comprehensive solution that combines the features according to the present disclosure.
  • a hydrogen-rich gaseous product e.g., a product comprising at least 98% hydrogen gas
  • other valuable product(s) is obtained from the gaseous byproduct resulting from the treatment of the contaminated water.
  • a system is provided for treating contaminated water according to the present disclosure, comprising a titanium anode comprising a mixed metal oxide (MMO) coating, a titanium cathode, a channel between the anode and the cathode, and a power source to apply electricity across the channel, or to the anode and/or cathode.
  • MMO mixed metal oxide
  • the system comprises a plurality of anodes and a plurality of cathodes.
  • the MMO coating is iridium oxide.
  • the MMO coating comprises iridium oxide, ruthenium oxide, tantalum oxide, and platinum oxide.
  • the titanium cathode comprises an MMO coating.
  • a method which comprises at least the following steps: (1) treating contaminated water, wherein said treating produces a gaseous byproduct that comprises hydrogen gas and at least one other gas; and (2) removing the at least one other gas(es) from the gaseous byproduct to produce a hydrogen-rich gaseous product.
  • the method may further comprise a step (3) in which the hydrogen-rich gaseous product is used as fuel for a device configured to produce electricity from the hydrogen-rich gaseous product.
  • the electricity produced by the device may, in some embodiments, may be used to power the treatment of contaminated water that occurs in step (1).
  • the hydrogen-rich gaseous product comprises 98% or more or 99% or more hydrogen gas.
  • the gaseous byproduct may comprise hydrogen and at least one gas selected from the following: a halogen gas (e.g., chlorine gas) or halogen-containing gas, oxygen gas, carbon dioxide gas, sulfur-containing gas, or any combinations thereof.
  • a halogen gas e.g., chlorine gas
  • the gaseous byproduct may comprise hydrogen gas, chlorine gas, and carbon dioxide gas.
  • treating the contaminated water comprises removing water-soluble organics (WSOs) or water-soluble organic compounds (WSOCs) from the contaminated water.
  • WSOs water-soluble organics
  • WSOCs water-soluble organic compounds
  • the gaseous byproduct comprises hydrogen gas and a halogen gas or halogen-containing gas (e.g., chlorine gas)
  • the halogen gas or halogen-containing gas e.g., chlorine gas
  • the gaseous byproduct may be removed from the gaseous byproduct using lime (CaO), soda lime (CaO and NaOH), activated alumina, or a mixture of calcium hydroxide and potassium hydroxide.
  • the gaseous byproduct comprises hydrogen gas and carbon dioxide gas
  • the hydrogen dioxide gas may be removed from the gaseous byproduct using an amine-containing material.
  • the gaseous byproduct comprises sulfur-containing gas, e.g.
  • a method comprises at least the following steps: (1) treating a petroleum refining effluent (PRE), wherein said treating produces a gaseous byproduct that comprises hydrogen gas, halogen gas or halogen-containing gas, carbon dioxide gas, and a sulfur-containing gas; (2) removing the halogen gas or halogen-containing gas, the carbon dioxide gas, and the sulfur-containing gas from the gaseous byproduct to produce a hydrogen- rich gaseous product; and (3) using the hydrogen-rich gaseous product to produce electricity.
  • PRE petroleum refining effluent
  • the halogen gas or halogen-containing gas may be removed using lime (CaO), soda lime (CaO and NaOH), activated alumina, or a mixture of calcium hydroxide and potassium hydroxide; the carbon dioxide gas may be removed using an amine-containing material; and the sulfur-containing gas may be removed using a caustic material.
  • Patent Application Docket No.067862.00033 In this method, treating a petroleum refining effluent (PRE) may involve removal of water-soluble organics (WSOs) or water-soluble organic compounds (WSOCs) from the petroleum refining effluent (PRE) using an electro-oxidation process.
  • WSOs water-soluble organics
  • WSOCs water-soluble organic compounds
  • the electricity produced using the hydrogen-rich gaseous product may be used to power the electro-oxidation process.
  • a system comprises at least the following subsystems: (1) a subsystem configured for treating contaminated water, wherein a gaseous byproduct comprising hydrogen and at least one other gas(es) is produced by treating the contaminated water; (2) a subsystem configured for removing the at least one other gas from the gaseous byproduct to produce a hydrogen-rich gaseous product.
  • the system includes a further subsystem as follows: (3) a subsystem configured for using the hydrogen-rich gaseous product to produce electricity.
  • the system may be configured to use the electricity produced in subsystem (3) to power subsystem (1), i.e., to power the treatment of the contaminated water.
  • the subsystem configured for removing the at least one other gas from the gaseous by product to produce a hydrogen-rich gaseous product may be made up of one or more units for performing this function. For example, a unit configured for removing halogen gas, a unit configured for removing sulfur-containing gas, and/or a unit configured for removing carbon dioxide gas.
  • the system comprises an electro-oxidation system/process including: a titanium anode coated with platinum, and a mixed metal oxide combination having two or more of ruthenium oxide, iridium(IV) oxide, tantalum oxide, or any combination thereof.
  • a mixed metal oxide, titanium anode and a titanium cathode connected to a voltage Patent Application Docket No.067862.00033 source.
  • the mixed metal oxide, titanium anode is specifically coated in a mixed metal oxide combination (two or more mixed metal oxides, namely, those having rare earth metal elements) and platinum (distinguished from platinum oxide; platinum is a noble metal)
  • a mixed metal oxide combination two or more mixed metal oxides, namely, those having rare earth metal elements
  • platinum distinguished from platinum oxide; platinum is a noble metal
  • an electro-oxidation system/process including a coated titanium anode and an equivalently coated titanium cathode connected to a voltage source is provided.
  • the anode and the cathode are coated in a mixed metal oxide, namely, any of ruthenium oxide, iridium(IV) oxide, tantalum oxide, or those listed above and herein.
  • an electro-oxidation system/process including a mixed metal oxide and platinum, titanium anode, and a mixed metal oxide and platinum, titanium cathode connected to a voltage source.
  • the mixed metal oxide and platinum, titanium electrodes each may specifically include a mixed metal oxide combination (two or more mixed metal oxides, namely, two or more of ruthenium oxide, iridium(IV) oxide, tantalum oxide, or those listed above and herein, or any combination thereof).
  • reversed polarity is used to defoul / descale the electrode that was once the anode and is now the cathode (after the reversal of polarity), such that the system/process does not have to be shut down or bypassed.
  • the electrodes are configured as a selectively replaceable cartridge that it is an easy replacement piece when the electrodes reach the end of their useful life.
  • Fig.1 is a schematic drawing of a simple bench scale test setup according to some embodiments described herein.
  • Fig.2 is a schematic drawing of systems and methods described herein where the gaseous byproduct contains hydrogen gas, a halogen or halogen-containing gas, carbon dioxide gas, and a sulfur-containing gas.
  • Fig.3 is a schematic drawing showing inputs and outputs of the three subsystems described herein.
  • Fig.4 is a schematic representation of an embodiment of subsystem (2) as described herein showing the separation of hydrogen and utilization in an embodiment of subsystem (3), e.g., PEM fuel cells, to generate electricity.
  • Fig.5A, Fig.5B, and Fig.5C include graphs showing GC analysis of gas samples collected during electro-oxidaiton (EO) according to some embodiments described herein.
  • Fig.6A, Fig.6B, and Fig.6C include graphs showing showing GC analysis of gas samples collected during electro-oxidaiton (EO) according to some embodiments described herein.
  • Fig.7A and Fig.7B include graphs showing showing GC analysis of gas samples collected during electro-oxidaiton (EO) according to some embodiments described herein.
  • Fig.8 is a hydrogen gas calibration chart DETAILED DESCRIPTION Patent Application Docket No.067862.00033 [0045]
  • the subject matter of aspects of the present disclosure is described with specificity herein to meet statutory requirements. However, the description itself is not intended to limit the scope of this patent. Rather, the inventors have contemplated that the claimed subject matter might also be embodied in other ways, to include different steps or combinations of steps similar to the ones described in this document, in conjunction with other present or future technologies.
  • Patent Application Docket No.067862.00033 [0049] Further, when the phrase “up to” is used in connection with an amount or quantity; it is to be understood that the amount is at least a detectable amount or quantity. For example, a material present in an amount “up to” a specified amount can be present from a detectable amount and up to and including the specified amount. [0050] Additionally, in any disclosed embodiment, the terms “substantially,” “approximately,” and “about” may be substituted with “within [a percentage] of” what is specified, where the percentage includes 0.1, 1, 5, and 10 percent. [0051] At a high level, embodiments of the present technology are directed towards processes, systems, and methods for treating contaminated waters, for instance, contaminated aqueous streams.
  • a contaminated aqueous stream is a discharge water stream that is emitted from a produced water facility, sometimes referred to as a dirty water facility, or from industrial production or processing facilities, for example, from oil or gas wells or from systems associated with or related to oil or gas wells.
  • water produced in these processes or that are considered discharge water for example water volumes or streams that are periodically or continuously discharged from these facilities (e.g. the ocean), may instead be pumped to in-land facilities, storage tanks or reservoirs, or to naturally occurring or natural substrate-based storage chambers or caverns.
  • embodiments of the technology described herein can provide multiple benefits compared to conventional systems, for instance, implementation of systems and/or processes described herein can be applied to contaminated waters like spent caustic-laden streams and per- and polyfluoroalkyl substance-laden streams and water-soluble organics (WSO)-laden streams.
  • Spent caustic streams as used herein refer to, for example, sodium hydroxide waste streams derived from the “scrubbing” of sulfur-containing natural gas.
  • Patent Application Docket No.067862.00033 Patent Application Docket No.067862.00033
  • embodiments of the technology described herein yield “green” and/or “blue” and/or “grey” hydrogen and allow for the production of like-type products using the hydrogen.
  • the method described herein may comprise, consist of, or consist essentially of the following steps: (1) a step of treating contaminated water, wherein a byproduct of said treating is a gaseous byproduct that comprises hydrogen and at least one other gas(es); and (2) a step wherein the at least one other gas(es) is/are removed from the gaseous byproduct, and a hydrogen-rich gaseous product is produced.
  • the method may further comprise, consist of, or consist essentially of an additional step (3). In this additional step (3), the hydrogen-rich gaseous product is used to produce electricity.
  • the hydrogen-rich gaseous product is used to produce electricity and the electricity is used to power the contaminated water treatment step (1).2.5% to as high as 70% of the electricity needed for the contaminated water treatment step may be supplied by using the hydrogen-rich gaseous product to produce electricity.
  • Step 1 In a first step of the method, contaminated water is treated, and the treatment of the contaminated water produces a gaseous byproduct that contains hydrogen gas and at least one other gas.
  • the term “contaminated water” as used herein is not so limited.
  • the contaminated water may be a petroleum refining effluent (PRE).
  • Petroleum refining effluent is the waste water discharged from petroleum refineries.
  • Petroleum refineries process raw crude oil into three categories of products: (1) fuel Patent Application Docket No.067862.00033 products, which include gasoline, distillate fuel oil, jet fuels, residual fuel oil, liquefied petroleum gases, refinery fuel, coke, and kerosene; (2) nonfuel products, which include asphalt and road oil, lubricants, naphtha solvents, waxes, nonfuel coke, and miscellaneous products, and (3) petrochemicals and petrochemical feedstocks including naphtha, ethane, propane, butane, propylene, butylene, and BTEX compounds (benzene, toluene, ethylbenzene, and xylene).
  • contaminated water may refer to water having one or more of the following components: hydrocarbons, phenols, ammonia, sulfides, organic and/or inorganic salts, PFAS, or any combination thereof.
  • the amount of water in the contaminated water may vary from 50% to 95%, from 50% to 90%, from 50% to 85%, from 50% to 80%, from 50% to 75%, from 50% to 70%, from 50% to 65%, from 50% to 60%, or from 50% to 55%.
  • the amount of hydrocarbons in the contaminated water may range from 0.005% to 15%, from 0.005% to 14%, from 0.005% to 13%, from 0.005% to 12%, from 0.005% to 11%, from 0.005% to 10%, from 0.005% to 9%, from 0.005% to 8%, from 0.005% to 7%, from 0.005% to 6%, from 0.005% to 5%, from 0.005% to 4%, from 0.005% to 3%, from 0.005% to 2%, from 0.005% to 1%, or from 0.01% to 10%.
  • Amounts of ammonia may vary from 0.005% to 5%, from 0.005% to 4%, from 0.005% to 3%, from 0.005% to 2%, from 0.005% to 1%, or from 0.01% to 1%.
  • Amounts of organic and/or inorganic salts may vary from 1% to 35%, from 1% to 30%, from 1% to 25%, from 1% to 20%, from 1% to 15%, from 1% to 10%, from 1% to 5%, or from 5% to 25%.
  • Amounts of sulfides may range from 0.05% to 10 %, from 0.05% to 9 %, from 0.05% to 8%, from 0.05% to 7 %, from 0.05% to 6 %, from 0.05% to 5 %, from 0.05% to 4 %, from 0.05% to 3 %, from 0.05% to 2 %, from 0.05% to 1 %, or from 0.1% to 6 %.
  • Per- and polyfluoroalkyl substances may be present in amounts ranging from 1 to 10,000 parts per trillion, from 1 to 10,000 parts per trillion, from 1 to 9,000 parts per trillion, from 1 to 8,000 parts per trillion, from 1 to 7,000 parts Patent Application Docket No.067862.00033 per trillion, from 1 to 6,000 parts per trillion, from 1 to 5,000 parts per trillion, from 1 to 4,000 parts per trillion, from 1 to 3,000 parts per trillion, from 1 to 2,000 parts per trillion, from 1 to 1,000 parts per trillion, from 1 to 750 parts per trillion, from 1 to 500 parts per trillion, from to 1 250 parts per trillion, from 1 to 100 parts per trillion, or from 1 to 50 parts per trillion.
  • PFAS Per- and polyfluoroalkyl substances
  • the contaminated water preferably has a salt content of about 2,000 ⁇ 500 ppm to 300,000 ⁇ 500ppm or from about 2,500 ⁇ 500 ppm to 250,000 ⁇ 500ppm or. Salt content changes the resistivity/conductivity of the contaminated water. In one aspect, the system can tolerate salt contents as low as from about 25.0 ppm to about 2,000.0 ⁇ 500ppm.
  • Treating contaminated water in some instances, may comprise, consist of, or consist essentially of removing one or more of the components mentioned in the preceding paragraph from the contaminated water.
  • treating may comprise, consist of, or consist essentially of partially, substantially, or completely removing hydrocarbons, phenols, ammonia, sulfides, organic and/or inorganic salts, PFAS, or any combination of the foregoing from the contaminated water.
  • treating contaminated water may comprise, consist of, or consist essentially of the addition of components to the contaminated water.
  • components may be added to customize and/or enhance the generation of hydrogen and/or other byproducts of value.
  • addition of components that increase the hydroxyl radical concentration of the contaminated water may be added.
  • demulsifiers may be added to the contaminated water to separate the organics.
  • treating the contaminated water may comprise, consist of, or consist essentially of removing water-soluble organics (WSOs) or water-soluble organic compounds (WSOCs) from the contaminated water. All hydrocarbons will partition to some extent to the water phase, i.e., they will dissolve to at least some extent in the water. Some species, including aromatics such as benzene, toluene, ethylbenzene, and xylene, partition or become dissolved in the water in measurable quantities.
  • WSOs water-soluble organics
  • WSOCs water-soluble organic compounds
  • treating contaminated water to remove water-soluble organics (WSOs) or water-soluble organic compounds (WSOCs) from the contaminated water comprises, consists of, or consists essentially of an electro-oxidation process.
  • Electro-oxidation is a process of treating contaminated water by employing an oxidative reaction at the electrode surface to break down and remove organic and inorganic pollutants present in water. Electric current is applied to water which leads to the formation of oxidative species like hydroxyl radicals.
  • the inorganic and organic pollutants present in water are oxidized and in turn the water is purified of these impurities.
  • hydrogen gas is produced along with other gases like carbon dioxide gas, oxygen gas, and chlorine gas depending on the pollutants in the contaminated water.
  • the electro-oxidation process utilizes an electro-oxidation (EO) unit.
  • the EO unit may comprise, consist of, or consist essentially of the following parts: inlet(s) that allow contaminated water to enter the EO unit, outlet(s) that allow treated water to exit the EO unit, a power supply, one or more pairs (i.e., one anode and one cathode), of electrodes, and a tank to hold the contaminated water while it is being treated.
  • the EO unit comprises one or more electrode pairs (i.e., an anode and a cathode) where the anode and the cathode are both Patent Application Docket No.067862.00033 made of titanium.
  • one or more of the electrode pairs may comprise an anode coated with a mixed metal oxide, including typically for example ruthenium oxide (RuO 2 ), iridium oxide (IrO2), or platinum oxide (PtO2).
  • a mixed metal oxide including typically for example ruthenium oxide (RuO 2 ), iridium oxide (IrO2), or platinum oxide (PtO2).
  • Mixed metal oxide electrodes also called dimensionally stable anodes, are devices with high conductivity and corrosion resistance for use as electrodes (specifically, anodes) in electrolysis. They are typically made by coating a substrate, such as a pure titanium plate or expanded mesh, with one or several kinds of metal oxides such as ruthenium oxide (RuO2), iridium(IV) oxide (IrO2), or platinum oxide (PtO2), which conducts electricity and catalyzes the reaction.
  • RuO 2 ruthenium oxide
  • IrO2 iridium oxide
  • PtO2 platinum oxide
  • Oxides containing two or more different kinds of metal cations are known as mixed metal oxides. Oxides can be binary, ternary and quaternary and so on with respect to the presence of the number of different metal cations. They can be further classified based on whether they are crystalline or amorphous. If the oxides are crystalline, then the crystal structure can determine the oxide composition. For instance, perovskites have the general formula ABO3; scheelites, ABO4; spinels, AB2O4; and palmeirites, A3B2O8.
  • MMO coatings typically consist of an electro-catalytic conductive component that catalyzes the reaction to generate current flow, and bulk oxides (cheaper fill materials) that prevent corrosion of the substrate material (titanium).
  • an electro-catalytic conductive component that catalyzes the reaction to generate current flow
  • bulk oxides that prevent corrosion of the substrate material (titanium).
  • one primary electro catalysts that can be used is ruthenium oxide.
  • Other oxides are a mixture of titanium dioxide (TiO2) and tantalum oxide (TaO5).
  • Titanium dioxide and/or tantalum oxide can further provide an oxide film over the substrate material (e.g., the titanium) to prevent corrosion of the substrate.
  • Patent Application Docket No.067862.00033 the polarity of the electrodes in the electrode pair (i.e., an anode and a cathode) may be reversed, i.e., the anode becomes the cathode and the cathode becomes the anode. Reversal of polarity may be used to defoul/descale the electrode that was once the anode and is now the cathode (after the reversal of polarity), such that the system/process does not have to be shut down or bypassed.
  • the electrodes are configured as a selectively replaceable cartridge that it is an easy replacement piece when the electrodes reach the end of their useful life.
  • the system/process is consistent in producing efficient and effective results (e.g., acceptable discharge water) even during maintenance and upkeep.
  • the system/process has a reduced size and footprint, a reduced weight, and a reduced capital expenditure and operating cost.
  • Voltage used in the electro-oxidation process is not so limited, and may range from about 0.5V to about 20V, from about 1V to about 20V, from about 1V to about 19V, from about 1V to about 18V, from about 1V to about 17V, from about 1V to about 16V, from about 1V to about 15V, from about 1V to about 14V, from about 1V to about 13V, from about 1V to about 12V, from about 1V to about 11V, from about 1V to about 10V, from about 1V to about 9V, from about 1V to about 8V, from about 1V to about 7V, from about 1V to about 6V, from about 1V to about 5V, rom about 1V to about 4V, from about 1V to about 3V, or from about 1V to about 2V.
  • the current density of the electro-oxidation process is preferably about 10 to 70 milliamps per square centimeter (mA/cm 2 ), most preferably in a ranged from about 20 to 60 mA/cm 2 , from about 30 to 60 mA/cm 2 , from about 40 to 60 mA/cm 2 , or from about 50 to 60 mA/cm 2 .
  • the voltage may need to be adjusted to achieve the desired current density. Contaminated water with lower salt content (i.e., contaminated water that is more resistive and less conductive) will require a higher voltage to Patent Application Docket No.067862.00033 achieve the desired current density.
  • Contaminated water with higher salt content i.e., contaminated water that is less resistive and more conductive
  • a minimum salt content of 2,500 ppm may be desired so that current density remains between about 20 to 60 mA/cm 2 when a voltage between 1-4 V is applied.
  • current densities from 25 to 60 mA/cm 2 are achieved using voltages less than 4V, e.g., about 3.8 V.
  • contaminated water entering the electro-oxidation unit may be monitored for its level of contamination, and voltage, current density, etc.
  • treating the water produces a gaseous byproduct that comprises, consists of, or consists essentially of hydrogen and at least one other gas.
  • the at least one other gas is selected from the following: halogen gas (e.g., chlorine gas, fluorine gas, iodine gas, and bromine gas), oxygen gas, carbon dioxide gas, sulfur-containing gas (e.g., hydrogen sulfide(H 2 S), sulfur dioxide (SO 2 )), or any combinations thereof.
  • the gaseous byproduct may comprise, consist of, or consist essentially of hydrogen gas and a halogen gas or halogen-containing gas, e.g., chlorine gas.
  • the gaseous byproduct may comprise, consist of, or consist essentially of hydrogen gas, a halogen gas or halogen-containing gas, e.g., chlorine gas, and a sulfur-containing gas, e.g., hydrogen sulfide.
  • the gaseous byproduct may comprise, consist of, or consist essentially of hydrogen gas, carbon dioxide, a halogen gas or halogen-containing, e.g., chlorine gas, and a sulfide-containing gas, e.g., hydrogen sulfide.
  • the gaseous byproduct may comprise, consist of, or consist essentially of hydrogen gas, carbon dioxide, oxygen gas, a halogen gas or halogen- containing gas, e.g., chlorine gas, and a sulfide-containing gas, e.g., hydrogen sulfide.
  • Patent Application Docket No.067862.00033 Collection of the gaseous byproduct in this step is important, and may be done by any acceptable means currently known or to be devised in the future. In an electro-oxidation process, gas may be collected on a cathode side. [0072] Transportation of the collected gaseous byproduct is also important, and may be done by any acceptable means currently known or to be devised in the future.
  • Step 2 gases other than hydrogen may be removed from the gaseous byproduct. This may be done by removing one or more of the non-hydrogen gases at a time. This may be done until mainly hydrogen gas remains, i.e., until the hydrogen-rich gaseous product remains.
  • the hydrogen-rich gaseous product is preferably at least 90% hydrogen, more preferably at least 95% hydrogen, even more preferably more than 98% hydrogen, and most preferably more than 99% hydrogen.
  • the gaseous byproduct comprises, consists of, or consists essentially of hydrogen and a halogen gas (i.e., chlorine gas, bromine gas, iodine gas, fluorine gas, or any combination thereof) or halogen-containing gas (e.g., HF, ClF3, SiF3, BrF3, BrF5, WF 6 , TiF 4 , BF 3 , MoF 6 , HCl, or any combination thereof), the halogen or halogen-containing gas may be partially or completely removed from the gaseous byproduct by any acceptable means currently known or to be devised in the future.
  • a halogen gas i.e., chlorine gas, bromine gas, iodine gas, fluorine gas, or any combination thereof
  • halogen-containing gas e.g., HF, ClF3, SiF3, BrF3, BrF5, WF 6 , TiF 4 , BF 3 , MoF 6 , HCl, or any combination thereof
  • removing the halogen or halogen-containing gas from the gaseous byproduct may involve the use of lime (CaO), soda lime (CaO and NaOH), activated alumina, or Patent Application Docket No.067862.00033 a mixture of calcium hydroxide and potassium hydroxide.
  • lime (CaO) is used, the resulting bleach salt byproducts, e.g., CaOCl, CaOBr, etc., are commercially desirable.
  • the gaseous byproduct comprises, consists of, or consists essentially of hydrogen and carbon dioxide gas
  • the carbon dioxide gas may be partially or completely removed by any acceptable means currently known or to be devised in the future.
  • an amine-containing material may be used to remove carbon dioxide.
  • the amine-containing material may be a monoethanolamine solution (20-30 wt.% in water) typically used in amine scrubbing, which allows for CO2 collection with high purity (often >99%).
  • Carbonate salts e.g., sodium bicarbonate, result from amine scrubbing processes.
  • Other examples of amine-containing materials that may be used are amine-functionalized materials, e.g., amine-functionalized porous support materials.
  • amine- functionalized porous support materials include, but are not limited to, amine-functionalized mesoporous silica, amine-functionalized fumed silica, amine-functionalized zeolite, amine- functionalized protonated titanate nanotubes (PTNTs), amine-functionalized nanoporous titanium oxyhydrate, amine-functionalized carbon nanotubes (CNTs), amine-functionalized PMMA, amine-functionalized silica gel, amine-functionalized PAN carbon fibers, amine- functionalized nanosilica, amine-functionalized TiO2, and the like.
  • the porous support materials may be “functionalized” by wet impregnation or anchoring on the surface with covalent bonds.
  • Amines used for functionalization of these porous support materials include tetraethylenepentamine (TEPA), triethylenetetramine (TETA), pentaethylenehexamine (PEHA), Polyethylenimine (PEI), ethylenepentamine (EPA), monoethanolamine, branched polyethylenimine (BPEI), diethylenetriamine (DETA), and linear polyethylenimine (LPEI).
  • TEPA tetraethylenepentamine
  • TETA triethylenetetramine
  • PEHA pentaethylenehexamine
  • PEI Polyethylenimine
  • EPA ethylenepentamine
  • BPEI branched polyethylenimine
  • DETA diethylenetriamine
  • LPEI linear polyethylenimine
  • Sulfur-containing gas comprises, consist of, or consists essentially of one or more selected from: hydrogen sulfide (H 2 S), sulfur dioxide (SO 2 ), dimethyl sulfide, methane thiol, dimethyl disulfide, and any combination thereof.
  • the sulfur-containing gas may be partially or completely removed from the gaseous byproduct using a caustic material.
  • the caustic material may be a caustic solution.
  • a caustic solution comprising NaOH, KOH, LiOH, ammonium hydroxide, and the like.
  • the removal of the gases other than hydrogen from the gaseous byproduct may be done in any order so long as the hydrogen-rich gaseous product may eventually be obtained.
  • a gaseous byproduct comprising, consisting of, or consisting essentially of hydrogen, carbon dioxide, a halogen gas or halogen-containing gas, and a sulfur-containing gas
  • the gases other than hydrogen may be removed in the following order: first remove halogen gas or halogen-containing gas, then remove carbon dioxide, and finally remove sulfur-containing gas.
  • the method may further comprise, consist of, or consist essentially of a third step (3) in which the hydrogen-rich gaseous product from step (2) is used as fuel for a device capable of producing electricity from the hydrogen-rich gaseous product.
  • the hydrogen-rich gaseous product may be used as fuel for a hydrogen fuel cell.
  • the hydrogen-rich gaseous product may be used as fuel for a hydrogen fuel cell, and electricity may be produced. In some embodiments, this electricity may be used to power the water treatment of step (1) of this method.
  • from about 2.5% to as high as 70% from about 20% to as high as about 70%, from about 20% to about 60%, from about 20% to about 50%, from about 20% to about 40%, from about 20% to about 30%, of the energy needed in the water treatment step may be provided using electricity produced from the hydrogen-rich gaseous product.
  • a system that comprises, consists of, or consists essentially of the following subsystems: (1) a subsystem configured for, capable of, and/or adapted to treat contaminated water, wherein a gaseous byproduct comprising hydrogen and at least one other gas is produced by treating the contaminated water; and (2) a subsystem configured for, capable of, and/or adapted to remove the at least one other gas from the gaseous byproduct to produce a hydrogen-rich gaseous product.
  • the system may further comprise, consist of, or consist essentially of a subsystem (3) that is configured for, capable of, and/or adapted to use the hydrogen-rich gaseous product to produce electricity.
  • the system may be configured for, capable of, and/or adapted to use the produced electricity from subsystem (3) to power the treatment of the contaminated water in subsystem (1).
  • the hydrogen-rich gaseous product may be used to produce 2.5% to 70% or as high as 20-70% of the electricity needed to power the treatment of the contaminated water in subsystem (1).
  • (1) subsystem 1- [0088]
  • the subsystem for treating contaminated water is not so limited. Any system for treating contaminated water that generates a gaseous by product as described herein (e.g., a gaseous by Patent Application Docket No.067862.00033 product comprising, consisting of, or consisting essentially of hydrogen gas and at least one other gas) may be subsystem 1 as described herein.
  • subsystem 1 may comprise, consist of, or consist essentially of an EO cell or EO unit as described herein.
  • a schematic drawing of an EO unit is shown in Fig.2.
  • the EO unit may comprise, consist of, or consist essentially of the following parts: inlet(s) that allow contaminated water to enter the EO unit, outlet(s) that allow treated water to exit the EO unit, a power supply, one or more pairs (i.e., one anode and one cathode), of electrodes, and a tank to hold the contaminated water while it is being treated.
  • the EO unit comprises one or more electrode pairs (i.e., an anode and a cathode) where the anode and the cathode are both made of titanium.
  • one or more of the electrode pairs may comprise an anode coated with a mixed metal oxide, including typically for example ruthenium oxide (RuO 2 ), iridium oxide (IrO 2 ), or platinum oxide (PtO2).
  • Mixed metal oxide electrodes also called dimensionally stable anodes, are devices with high conductivity and corrosion resistance for use as electrodes (specifically, anodes) in electrolysis.
  • Oxides containing two or more different kinds of metal cations are known as mixed metal oxides. Oxides can be binary, ternary and quaternary and so on with respect to the presence of the number of different metal cations. They can be further classified based on whether they are crystalline or amorphous. If the oxides are crystalline, then the crystal structure can determine the oxide composition.
  • perovskites have the general formula ABO3; scheelites, ABO4; spinels, AB2O4; and palmeirites, A3B2O8.
  • the different metal cations are Patent Application Docket No.067862.00033 present as MIn+-Ox and MIIn+-Ox polyhedra, which are connected in various possible ways, such as corner or edge sharing, forming chains MI–O–MII–O, MI–O–MI–O or MII–O–MII–O. Therefore, MMO coatings typically consist of an electro-catalytic conductive component that catalyzes the reaction to generate current flow, and bulk oxides (cheaper fill materials) that prevent corrosion of the substrate material (titanium).
  • An input to subsystem (1) may comprise, consist of, or consist essentially of contaminated water as described herein. See Fig.3.
  • Output of subsystem (1) may comprise, consist of, or consist essentially of a gaseous byproduct as described herein. See Fig.3.
  • subsystem (1) may further comprise sensors, e.g., sensors placed at the inlet(s), to monitor the level of contamination of the water.
  • the system may further be configured for, capable of, and/or adapted to adjust the applied voltage, the current density, etc. in response to the measured level of contamination to generate a gaseous byproduct with a larger or smaller percentage of hydrogen gas.
  • subsystem 2- may comprise, consist of, or consist essentially of one or more units for removing gases other than hydrogen from the gaseous byproduct.
  • the input of subsystem (2) comprises, consists of, or consists essentially of the gaseous byproduct from subsystem (1). See Fig.2 and Fig.3.
  • the units may be wet gas scrubber units that use liquid solutions to remove one or more gases other than hydrogen from the gaseous byproduct.
  • they may dry gas scrubber units that use solid sorbents to remove one or more gases other than hydrogen from the gaseous byproduct.
  • subsystem (2) may comprise, consist of, or consist essentially of a unit for removing halogen gas or halogen-containing gas from the gaseous byproduct.
  • the unit for removing halogen or halogen-containing gas from the gaseous byproduct may utilize lime (CaO), soda lime (CaO and NaOH), activated alumina, or a mixture of calcium hydroxide and potassium hydroxide for this purpose.
  • a unit utilizing a lime solution for this purpose would be a wet scrubber unit.
  • subsystem (2) may comprise, consist of, or consist essentially of a unit for removing carbon dioxide gas from the gaseous byproduct.
  • the unit may utilize an amine-containing material to remove carbon dioxide gas from the gaseous product.
  • the amine-containing material may be a monoethanolamine solution (20-30 wt.% in water) typically used in amine scrubbing, which allows for CO 2 collection with high purity (often >99%). Carbonate salts, e.g., sodium bicarbonate, result from amine scrubbing processes.
  • the unit may be a wet scrubber unit.
  • amine-containing materials that may be used are amine-functionalized materials, e.g., amine-functionalized porous support materials.
  • amine- functionalized porous support materials include, but are not limited to, amine-functionalized mesoporous silica, amine-functionalized fumed silica, amine-functionalized zeolite, amine- functionalized protonated titanate nanotubes (PTNTs), amine-functionalized nanoporous titanium oxyhydrate, amine-functionalized carbon nanotubes (CNTs), amine-functionalized PMMA, amine-functionalized silica gel, amine-functionalized PAN carbon fibers, amine- Patent Application Docket No.067862.00033 functionalized nanosilica, amine-functionalized TiO2, and the like.
  • the porous support materials may be “functionalized” by wet impregnation or anchoring on the surface with covalent bonds.
  • Amines used for functionalization of these porous support materials include tetraethylenepentamine (TEPA), triethylenetetramine (TETA), pentaethylenehexamine (PEHA), Polyethylenimine (PEI), ethylenepentamine (EPA), monoethanolamine, branched polyethylenimine (BPEI), diethylenetriamine (DETA), and linear polyethylenimine (LPEI).
  • the unit may be a dry scrubber unit that uses solid sorbents.
  • subsystem (2) may comprise, consist of, or consist essentially of a unit for removing sulfur-containing gas from the gaseous byproduct.
  • a caustic material may be used to partially or completely remove a sulfur-containing gas from the gaseous byproduct using a caustic material.
  • the caustic material may be a caustic solution.
  • a caustic solution comprising NaOH, KOH, LiOH, ammonium hydroxide, and the like.
  • the unit may be a wet scrubber unit.
  • Subsystem (2) may include other units for removing gases other than hydrogen from the gaseous byproduct.
  • Units may include more wet or dry scrubbing units, units utilizing gas separation membranes, and the like. Units may utilize different gas separation techniques including, but not limited to pressure swing absorption techniques, vacuum swing absorption techniques, temperature swing absorption techniques, and the like. [0102] The order or arrangement of the units in subsystem (2) is not so limited.
  • the units may be provided in the following order: unit for removing halogen gas or halogen-containing gas, and then unit for removing carbon dioxide; unit for removing halogen gas or halogen-containing gas, and then unit for removing carbon dioxide, and finally unit for Patent Application Docket No.067862.00033 removing sulfur-containing gas; unit for removing carbon dioxide, and then unit for removing halogen gas or halogen-containing gas; unit for removing carbon dioxide, and then unit for removing halogen or halogen-containing gas, and finally unit for removing sulfur-containing gas; unit for removing sulfur-containing gas, and then unit for removing carbon dioxide; unit for removing sulfur-containing gas, and then unit for removing halogen gas or halogen-containing gas; unit for removing sulfur-containing gas, and then unit for removing carbon dioxide, and finally unit for removing halogen gas or halogen-containing gas; or unit for removing sulfur- containing gas, and then unit for removing halogen gas or halogen-containing gas; or
  • subsystem (2) may further comprise, consist of, or consist essentially of units for removing solid particles and/or liquid droplets from the gaseous byproduct.
  • the units for removing solid particles and/or liquid droplets may be an electrostatic precipitator or some other unit that accomplishes the same or similar function.
  • the output of subsystem (2) may comprise, consist of, or consist essentially of a hydrogen-rich gaseous product. See Fig.3.
  • the hydrogen-rich gaseous product is suitable for use a fuel for a device such as a hydrogen fuel cell.
  • Subsystem (3) comprises, consists of, or consists essentially of a device for converting the hydrogen-rich gaseous product into electricity.
  • the input for subsystem (3) may comprise, consist of, or consist essentially of the hydrogen-rich product from subsystem (2).
  • the device is a hydrogen fuel cell.
  • the input for subsystem (3) may comprise, consist of, or consist essentially of the hydrogen-rich product from subsystem (2) and oxygen gas.
  • Patent Application Docket No.067862.00033 [0107]
  • the hydrogen fuel cell may comprise, consist of, or consist essentially of at least the following components, an anode, a cathode, and an electrolyte membrane.
  • subsystem (3) may comprise, consist of, or consist essentially of electricity. See Fig.3. In some embodiments, this electricity may be used to power subsystem (1).
  • Subsystem (3) may provide from about 2.5% to about 70%, from about 20% to 70% from about 20% to about 60%, from about 20% to about 50%, from about 20% to about 40%, or from about 20% to about 30%, of the electricity needed to power subsystem (1).
  • the test setup comprises: [0117] Conducted as a batch process on a bench scale. [0118]
  • the test water formulations contain the below chemicals/organics at various concentrations: • 85-99% Water • Diesel • Petrol • Tar/Bitumen • Soap as a surfactant • Sodium Chloride • Sodium Carbonate [0119] 1-gallon plastic tank with a removable lid on top and 1 ⁇ 2” outlet plastic tubing connector at the bottom of the tank with a valve. This is the feed tank.
  • the test water mixed with the organics Patent Application Docket No.067862.00033 is poured into the feed tank. A stirrer on the tank mixes the water well so a strong emulsion is made.
  • the anode and cathode plates are provided and will have specific coatings and metallurgy.
  • the anode and cathode are connected to a DC power supply through a 0-30 VDC (0-30 amps) rectifier power supply.
  • the cell(s) are immersed (1-2-gallon capacity in that the effective working volume for the cells to be completely immersed). It has an 1 ⁇ 2” Inlet Nozzle, 1 ⁇ 2” Outlet nozzle at the bottom, and an air-tight lid (that can open and close) so the cell can be cleaned after each test.
  • the cell has a 4” vent with a valve for the off-gas.
  • This off-gas during the test contains hydrogen, chlorine, and CO 2 , which are byproducts of electro-oxidation. These gases are mostly generated at the cathode side.
  • the off-gases are at atmospheric pressure. Hydrogen is separated and purified from these off-gases. The separated hydrogen and purity is quantified. [0125] Hydrogen separation is done using a silver palladium membrane or through pressure swing absorption. Patent Application Docket No.067862.00033 [0126] The separated hydrogen is feed to a Proton Exchange Fuel Cell Membrane. The other feed can be air (oxygen). The byproduct water is reused or drained [0127] The current generated and efficiency are quantified.
  • Phase I Details A simple bench scale test setup is fabricated.
  • the test water contains 85-99% Water, and traces of diesel, Petrol, Tar/ Bitumen, Soap as Surfactant, Sodium Chloride and Sodium Carbonate.
  • Patent Application Docket No.067862.00033 [0135]
  • the feed is passed through filter cartridge canister and the filtered waters flows to the Test Electro-Oxidation Cell (EO Cell) by gravity.
  • EO Cell Test Electro-Oxidation Cell
  • Evaluation of performance of the Electro-oxidation cells is done at various ranges of TDS in the Feed.
  • the TDS Content are in the range of 3%-10%.
  • TOC content in the range of 0.5 – 5%.
  • TOC/TDS of the feed stream are monitored regularly for the test.
  • the anode and cathode plates will have specific coatings and metallurgy.
  • the anode and cathode are connected to a DC power supply through a 0-30 VDC (0-30 amps) rectifier power supply.
  • the gas is collected from the cathode side.
  • Off-gas during the test is collected and tested.
  • the clean treated water from the EO cell is filtered through a carbon filter canister and drained.
  • Phase II Details [0142] After completing Phase, I and assessing the hydrogen recovery potential, Phase II commenced as follows: [0143] The hydrogen is separated and purified from the off-gases. Hydrogen separation is done using either silver palladium membrane or through pressure swing absorption. Patent Application Docket No.067862.00033 [0144] Exchange Fuel Cell Membrane. The other feed can be air (oxygen). The byproduct water can be reused or drained. [0145] The current generated and efficiency are quantified.
  • Test parameters • TDS/Conductivity of water • Current generated/voltage applied on EO cells • TDS/conductivity of water • Current generated/voltage applied on EO cells • Quantity of off-gas • H 2 content in off-gas • H2 content after purification • Other monitoring parameters on PEFM cell including current and voltage generated • Quantification of Electricity and efficiency. [0147] Therefore, the following is claimed:1. A system for hydrogen as described herein; 2. A method for hydrogen, as described herein; 3. A device for hydrogen as described herein; 4. A method of using a system or device for hydrogen as described herein;5. A method of using hydrogen from a system or device for hydrogen as described herein.
  • Electro-oxidation is a process of treating wastewater by employing an oxidative reaction at the electrode surface to break down and remove organic and inorganic pollutants present in water. Electric current is applied to water which leads to the formation of oxidative species like hydroxyl radicals. Using the oxidizing agents, the inorganic and organic pollutants present in water are oxidized and in turn the water is purified of these impurities.
  • hydrogen gas is produced including other gases like carbon dioxide gas, oxygen gas, and chlorine gas depending on the pollutants in the waste water. The hydrogen produced during the treatment of wastewater can be collected, purified, and used for energy production with the help of fuel cells.
  • the objectives are to assess the rate of hydrogen evolution during the electro-oxidation treatment of industrial waste water and use them in the fuel cell to produce electricity.
  • hydrogen released from the electro-oxidation process is quantified.
  • the purification and conversion of hydrogen into electricity are examined.
  • Phase IA Objective [0151] To quantify the amount of hydrogen produced and purity at various test parameters.
  • Phase IA Experimental Plan [0153] An Electro-oxidation (EO) cell or EO unit is constructed (MOC: borosilicate glass) with due consideration to the safety. Electrodes and a rectifier were provided to supply power.
  • EO Electro-oxidation
  • MOC borosilicate glass
  • the controllers in the rectifier have provisions to adjust the voltage and current.1.2 L of the sample was filled in the EO cell or EO unit, and required voltage was applied to generate the hydrogen.
  • Simulated wastewater samples having compositions as shown in Table 1 were prepared and used in the analysis: [0155] Table 1. Sample Composition Chemical Sample 1 Sample 2 % composition (mass %) % composition (mass %) NaCl 3.5 3.5 Na 2 CO 3 2.0 2.0 Na2SO4 2.5 2.5 CaSO4 1.5 1.5 Gasoline 0.1 Diesel 0.05 Water 90.5 90.35 Patent Application Docket No.067862.00033 [0156] The gas produced from the EO process is collected in a Tedlar® bag and the sample for GC analysis was taken in serum bottles.
  • Fig.5A, Fig.5B, and Fig.5C show the results obtained.
  • Fig.5A, Fig.5B, and Fig.5C include graphs showing GC analysis of gas samples collected during EO of sample 1 at different time.
  • Fig.5B Gas sample collected after 1 hour
  • Fig.5C Gas sample collected at after 2 hours.
  • Table 3 shows the composition and flow rates of gas produced during EO of sample 1 at different time.
  • Phase IIA Project Details One of the effective ways of treating dissolved organics present in the effluent water from the petroleum industry is electro-oxidation and the electro-oxidation of effluent water produces hydrogen along with chlorine, oxygen and carbon dioxide. This phase aims to remove other gases and utilize hydrogen in a proton exchange membrane (PEM) fuel cell to generate electricity.
  • PEM proton exchange membrane
  • a method comprising: (1) treating contaminated water, wherein treating contaminated water produces a gaseous byproduct that comprises hydrogen gas and at least one other gas; and (2) removing the at least one other gas from the gaseous byproduct to produce a hydrogen-rich gaseous product.
  • the hydrogen-rich gaseous Patent Application Docket No.067862.00033 product may comprise hydrogen gas in an amount of 99% or more.
  • the gaseous byproduct may comprise hydrogen gas and at least one other gas selected from: halogen gas or halogen-containing gas, oxygen gas, carbon dioxide gas, sulfur-containing gas, or any combinations thereof.
  • the gaseous byproduct may comprise hydrogen gas, halogen gas or a halogen-containing gas, carbon dioxide gas, and a sulfur-containing gas.
  • treating the contaminated water may comprise removing water-soluble organics (WSOs) or water-soluble organic compounds (WSOCs) from contaminated water.
  • the contaminated water may be a petroleum refining effluent (PRE).
  • the gaseous byproduct comprises halogen gas or halogen-containing gas
  • the halogen gas or halogen- containing may be removed using lime (CaO), soda lime (CaO and NaOH), activated alumina, or a mixture of calcium hydroxide and potassium hydroxide.
  • the carbon dioxide gas when the gaseous byproduct comprises carbon dioxide gas, the carbon dioxide gas may be removed using an amine-containing material.
  • the gaseous byproduct when the gaseous byproduct comprises a sulfur- containing gas, the sulfur-containing gas may be removed using a caustic material.
  • the hydrogen-rich gaseous product may be used as fuel for a device capable of producing electricity from the hydrogen-rich gaseous product.
  • a method comprising: (1) treating a petroleum refining effluent (PRE), wherein treating petroleum effluent (PRE) produces a gaseous byproduct that comprises hydrogen gas, a halogen or halogen-containing gas, carbon dioxide gas, and a sulfur- containing gas; and (2) removing the halogen gas or halogen-containing gas, the carbon dioxide gas, and the sulfur-containing gas from the gaseous byproduct to produce a hydrogen-rich gaseous product; and (3) using the hydrogen-rich gaseous product to produce electricity.
  • PRE petroleum refining effluent
  • the halogen gas or halogen-containing gas may be removed using lime (CaO), soda lime Patent Application Docket No.067862.00033 (CaO and NaOH), activated alumina, or a mixture of calcium hydroxide and potassium hydroxide; the carbon dioxide gas may be removed using an amine-containing material; and the sulfur-containing gas may be removed using a caustic material.
  • treating a petroleum refining effluent (PRE) may involve removal of water-soluble organics (WSOs) or water-soluble organic compounds (WSOCs) from the petroleum refining effluent (PRE) using an electro-oxidation process.
  • WSOs water-soluble organics
  • WSOCs water-soluble organic compounds
  • the electricity may be used to power an electro- oxidation process.
  • a method comprising: 1) treating a petroleum refining effluent (PRE), wherein treating petroleum refining effluent (PRE) produces a gaseous byproduct that comprises hydrogen gas, a halogen or halogen-containing gas, carbon dioxide gas, and a sulfur-containing gas; and (2) removing the halogen gas or halogen-containing gas, the carbon dioxide gas, and the sulfur-containing gas from the gaseous byproduct to produce a hydrogen- rich gaseous product; (3) using the hydrogen-rich gaseous product to produce electricity; and (4) using the electricity to power treating petroleum refining effluent (PRE).
  • PRE petroleum refining effluent
  • the halogen gas or halogen-containing gas may be removed using lime (CaO), soda lime (CaO and NaOH), activated alumina, or a mixture of calcium hydroxide and potassium hydroxide; the carbon dioxide gas may be removed using an amine-containing material; and the sulfur- containing gas may be removed using a caustic material.
  • treating a petroleum refining effluent (PRE) may involve removal of water-soluble organics (WSOs) or water-soluble organic compounds (WSOCs) from the petroleum refining effluent (PRE) using an electro- oxidation process.
  • WSOs water-soluble organics
  • WSOCs water-soluble organic compounds
  • a system comprising: (1) a subsystem configured for treating contaminated water, wherein a gaseous byproduct comprising hydrogen and at least one Patent Application Docket No.067862.00033 other gas is produced by treating the contaminated water; and (2) a subsystem configured for removing the at least one other gas from the gaseous byproduct to produce a hydrogen-rich gaseous product.
  • it may further comprise a subsystem (3) configured to use the hydrogen-rich gaseous product to produce electricity.
  • the system may be configured to use the electricity to power treating of the contaminated water.
  • the subsystem configured for removing the at least one other gas from the gaseous byproduct to produce a hydrogen-rich gaseous product may comprise a unit configured for removing a halogen gas or a halogen-containing gas.
  • the subsystem configured for removing the at least one other gas from the gaseous byproduct to produce a hydrogen-rich gaseous product may comprise a unit configured for removing carbon dioxide gas.
  • the subsystem configured for removing the at least one other gas from the gaseous byproduct to produce a hydrogen-rich gaseous product may comprise a unit configured for removing sulfur- containing gas.
  • a system comprising: (1) a subsystem configured for treating contaminated water, wherein a gaseous byproduct comprising hydrogen and at least one other gas is produced by treating the contaminated water; (2) a subsystem configured for removing the at least one other gas from the gaseous byproduct to produce a hydrogen-rich gaseous product; and (3) a subsystem configured to use the hydrogen-rich gaseous product to produce electricity.
  • the system may be configured to use the electricity to power treating of the contaminated water.
  • the subsystem configured for removing the at least one other gas from the gaseous byproduct to produce a hydrogen-rich gaseous product may comprise a unit configured for removing a halogen gas or a halogen-containing gas.
  • the subsystem configured for removing the at least one other gas from the gaseous Patent Application Docket No.067862.00033 byproduct to produce a hydrogen-rich gaseous product may comprise a unit configured for removing carbon dioxide gas.
  • the subsystem configured for removing the at least one other gas from the gaseous byproduct to produce a hydrogen-rich gaseous product may comprise a unit configured for removing sulfur-containing gas.
  • a system comprising: (1) a subsystem configured for treating petroleum refining effluent (PRE), wherein a gaseous byproduct comprising hydrogen gas, a halogen gas or halogen-containing gas, and a sulfur-containing gas is produced by treating the petroleum refining effluent (PRE); (2) a subsystem configured for removing the halogen gas or the halogen-containing gas, and the sulfur-containing gas from the gaseous byproduct to produce a hydrogen-rich gaseous product; and (3) a subsystem configured to use the hydrogen- rich gaseous product to produce electricity.
  • PRE petroleum refining effluent
  • the subsystem for treating petroleum refining effluent may comprise one or more pairs of Ti-containing electrodes. At least one of the one or more pairs of Ti-containing electrodes may comprise an anode coated with a mixed metal oxide.
  • the subsystem configured for removing the halogen gas or the halogen-containing gas, and the sulfur-containing gas from the gaseous byproduct to produce a hydrogen-rich gaseous product may comprise a unit configured for removing the halogen gas or halogen-containing gas.
  • the unit configured for removing the halogen gas or halogen-containing gas may comprise lime (CaO), soda lime (CaO and NaOH), activated alumina, or a mixture of calcium hydroxide and potassium hydroxide.
  • the subsystem configured for removing the halogen gas or the halogen-containing gas, and the sulfur-containing gas from the gaseous byproduct to produce a hydrogen-rich gaseous product may comprise a unit configured for removing the carbon dioxide gas.
  • the unit configured for removing carbon dioxide gas may comprise an amine-containing material.
  • a subsystem configured for removing the Patent Application Docket No.067862.00033 halogen gas or the halogen-containing gas, and the sulfur-containing gas from the gaseous byproduct to produce a hydrogen-rich gaseous product may comprise a unit configured for removing the sulfur-containing gas.
  • the unit configured for removing sulfur-containing gas may comprise a caustic material.
  • the subsystem configured to use the hydrogen-rich gaseous product to produce electricity may comprise a hydrogen fuel cell.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Electrochemistry (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne des systèmes et des procédés de traitement d'eau contaminée utilisée en tant que source d'hydrogène. Un sous-produit gazeux contenant du gaz hydrogène issu du traitement de l'eau contaminée est collecté, et des gaz autres que l'hydrogène sont éliminés de celui-ci pour former un produit gazeux riche en hydrogène. Le produit gazeux riche en hydrogène peut ensuite être utilisé comme combustible d'alimentation dans l'étape de traitement d'eau contaminée.
PCT/US2024/036304 2023-06-30 2024-06-30 Systèmes et procédés de traitement d'eau contaminée utilisée en tant que source d'hydrogène Pending WO2025007088A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202363524443P 2023-06-30 2023-06-30
US63/524,443 2023-06-30
US18/759,948 2024-06-30
US18/759,948 US20250002379A1 (en) 2023-06-30 2024-06-30 Systems and methods for treating contaminated water as a source for hydrogen

Publications (1)

Publication Number Publication Date
WO2025007088A1 true WO2025007088A1 (fr) 2025-01-02

Family

ID=93939964

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/036304 Pending WO2025007088A1 (fr) 2023-06-30 2024-06-30 Systèmes et procédés de traitement d'eau contaminée utilisée en tant que source d'hydrogène

Country Status (2)

Country Link
US (1) US20250002379A1 (fr)
WO (1) WO2025007088A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160045841A1 (en) * 2013-03-15 2016-02-18 Transtar Group, Ltd. New and improved system for processing various chemicals and materials
US20230159357A1 (en) * 2021-03-21 2023-05-25 James Lamar Dice ParaDice Process System

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160045841A1 (en) * 2013-03-15 2016-02-18 Transtar Group, Ltd. New and improved system for processing various chemicals and materials
US20230159357A1 (en) * 2021-03-21 2023-05-25 James Lamar Dice ParaDice Process System

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ABDALRHMAN ABDALLATIF SATTI, ZHANG YANYAN, ARSLAN MUHAMMAD, GAMAL EL-DIN MOHAMED: "Low-current electro-oxidation enhanced the biodegradation of the recalcitrant naphthenic acids in oil sands process water", JOURNAL OF HAZARDOUS MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 398, 1 November 2020 (2020-11-01), AMSTERDAM, NL , pages 122807, XP093255945, ISSN: 0304-3894, DOI: 10.1016/j.jhazmat.2020.122807 *

Also Published As

Publication number Publication date
US20250002379A1 (en) 2025-01-02

Similar Documents

Publication Publication Date Title
US7713399B2 (en) Process for treating a sulfur-containing spent caustic refinery stream using a membrane electrolyzer powered by a fuel cell
Rocha et al. Application of electrochemical oxidation as alternative treatment of produced water generated by Brazilian petrochemical industry
Bian et al. Oily bilge water treatment using DC/AC powered electrocoagulation
US11318416B2 (en) Conversion of gas and treatment of a solution
Cerqueira et al. Effects of direct and alternating current on the treatment of oily water in an electroflocculation process
JP2022535730A (ja) 分離および電気化学的排除を使用したｐｆａｓ処理スキーム
Ntagia et al. Electrochemical treatment of industrial sulfidic spent caustic streams for sulfide removal and caustic recovery
BRPI0713084A2 (pt) método e sistema integral para tratamento de águas para as torres de resfriamento e processos que requerem a eliminação da sìlica da água
WO1999034895A1 (fr) Procede electrolytique de traitement de flux de dechets aqueux
US20240300833A1 (en) Electrochemical conversion to carbonate-containing compounds and related methods
Rubach et al. Onshore testing of produced water by electroflocculation
Jawad et al. Treatment of petroleum refinery wastewater by electrochemical oxidation using graphite anodes
US20130008858A1 (en) Systems and Methods for Process Stream Treatment
CA3027250A1 (fr) Methodes et systemes de traitement de l'eau par floculation
US20250002379A1 (en) Systems and methods for treating contaminated water as a source for hydrogen
JP2010530793A (ja) プロセス流れ処理のためのシステム及び方法
KR20200103327A (ko) 휘발성 유기 화합물 처리 시스템
KR20200110535A (ko) 담수화 시스템
US20250326665A1 (en) Systems and methods for separating and removing water soluble organicsfrom aqueous streams
Galedari et al. Optimizing the combined electrocoagulation (EC) and electrochemical oxidation (EO) for treating the petroleum wastewater from crude oil storage tank bottoms
US20240360012A1 (en) Systems and methods for separating and/or removing water soluble organics from aqueous streams
Ntagia et al. Electrochemical removal of sulfur pollution
KR100411815B1 (ko) 전극을 이용한 유·무기물 함유폐수의 전기화학적유·무기물 제거방법 및 그 장치
CN1594123A (zh) 炼油废碱液处理方法
Aabid et al. Electrocoagulation Coupled Fenton Process for Treating Refinery Wastewater Using a Cylindrical Design of Ti and Al Electrodes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24833120

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)